CN105505618A - Sulfonate group-containing copolymers and manufacturing method thereof - Google Patents

Abstract

The objective of the invention is to provide detergent compositions with superior surfactant deposition-inhibiting ability and anti-gelling properties that exhibit good cleaning effectiveness even when laundering under harsh conditions such as laundering in residual bath water. A laundry detergent or cleaning composition which comprises a copolymer containing sulfonate groups containing from 1 to 50 mass% of structural units (a) derived from one or more kinds of monomers (A) selected from ether bond-containing monomers represented by formulas (1) and (2), 50 mass% or more and less than 98 mass% of structural units (b) derived from a carboxyl group-containing monomer (B), and 1 mass% or more and less than 50 mass% of structural units (c) derived from a sulfonate group-containing monomer (C).

Description

Containing the multipolymer and preparation method thereof of sulfonate group

The application's to be the applying date be September 1, denomination of invention in 2009 is the divisional application of the Chinese patent application No.200980142713.9 of " multipolymer and preparation method thereof containing sulfonate group ".

Technical field

The present invention relates to the multipolymer and preparation method thereof containing sulfonate group.

Background technology

Past, by detergent builder (washing composition auxiliary) if zeolite, carboxymethyl cellulose or polyethylene glycol blending are to in the washing composition of clothes washing, to reach the object improving washing composition cleaning efficacy.

Except above-mentioned various detergent builder, also polymkeric substance is blended in detergent composition as washing assistant in recent years.

Such as, use the multipolymer of acrylate and 3-allyloxy-2-hydroxyl-1-propanesulfonate, wherein at least one main chain terminal has sulfonate group, detergent builder as has been publicly (patent reference 1).

With regard to the ability needed for detergent builder, the ability improving washing composition cleaning efficacy is significant need.But current, also need the ability (hereafter also referred to as " deposition rejection ability ") suppressing/prevent surfactant deposition, surfactant deposition causes cleaning efficacy to reduce.Herein, surfactant deposition problem looms large when using harder water washing clothing, because its is for linear alkyl benzene sulphonic acid (salt) (LAS) of anion surfactant is as the result (see non-patent type with reference to 1) of the calcium ion existed in Witco 1298 Soft Acid (salt) and water or magnesium ion bonding.

The technique improving deposition rejection ability can referenced patents reference 2.Patent reference 2 illustrates, comprises the polyoxyalkylene compounds of alkyl and the graft copolymer obtained shows excellent properties as detergent builder with the unsaturated monomer graft polymerization comprising acidic-group of specified quantitative.

Because human consumer strengthens the consciousness of environmental problem in recent years, start to set up Novel clothes mode of washing, as human consumer economizes on water by using residue bath water washing clothes.In addition, the performance needed for detergent builder is also in change.Namely owing to using residue bath water, the problem that clothes washing must complete under the condition very high in the hardness caused due to Calcium compounds concentration is exposed.At this moment, even if need also to suppress deposition under high rigidity clothes washing condition and effective reagent, described reagent has than so-called antigelation characteristic even higher needed for the past.

From making the demand of detergent composition densification, provide the demand of multiple desired properties also to increase to a kind of component simultaneously.

reference listing

patent documentation

[PTL1] Japanese patent publication (Kokai) No.2002-3535

[PTL1] Japanese patent publication (Kokai) No.2007-254679

non-patent type document

[NPL1] LouisHoTanTai, " FormulatingDetergentsandPersonalCareProducts ", AOCSPress, 53-54 page (2000)

summary of the invention

technical problem

As mentioned above, although reported multiple polymers in the past, in fact there is not the polymkeric substance showing gratifying deposition rejection ability when being used for clothes washing.Therefore, the present invention carries out under above-mentioned background, and the object had is to provide the polymkeric substance (or polymer composition) that effectively can suppress surfactant deposition when being used for clothes washing.

Another object of the present invention is to provide the method effectively can preparing this base polymer (or polymer composition).

the method of dealing with problems

The present inventor finds when implementing careful and insistent research to realize above-mentioned purpose to various polymer/copolymer, wherein introduces with specific ratios and has excellent deposition rejection ability (suppressing/prevent the ability of surfactant deposition) derived from the structural unit of the special ether-containing key monomer of relative hydrophobicity, carboxyl group-containing monomer structural unit and the multipolymer (comprising the multipolymer of sulfonate group) derived from the structural unit containing sulfonate group monomer.Based on above-mentioned discovery, achieve the present invention.

Namely the present invention relates to the multipolymer comprising sulfonate group, but described multipolymer comprises 1 quality % or more is less than the structural unit (a) derived from one or more monomers (A) of 50 quality %, 50 quality % or more are still less than the structural unit (b) derived from carboxyl group-containing monomer (B) of 98 quality %, with 1 quality % or more but be less than 50 quality % derived from containing the structural unit (c) of sulfonate group monomer (C) as essentially consist unit, the ether-containing key monomer that described monomer (A) selects free style (1) and (2) to represent,

In described formula, R _orepresent hydrogen atom or CH ₃group, R represents CH ₂group, CH ₂cH ₂group or singly-bound, X represents the number (precondition is that then X represents the number of 1-5 if R is singly-bound) of 0-5, and R ₁for hydrogen atom or C1 to C20 organic group,

In described formula, R ₀represent hydrogen atom or CH ₃group, R represents CH ₂group, CH ₂cH ₂group or singly-bound, X represents the number of 0-5, and R ₁for hydrogen atom or C1 to C20 organic group.

beneficial effect of the present invention

Excellent deposition rejection ability (suppressing/prevent the ability of surfactant deposition) is shown containing sulfonate group multipolymer (or polymer composition of the present invention) due to of the present invention, if therefore use of the present invention containing sulfonate group multipolymer in detergent compositions, then effectively can suppress surfactant deposition.

embodiment describes

Hereafter illustrate in greater detail the present invention.

In the de-scription, " Cx to Cy organic group " (x and y represents numeral respectively) refers to the organic group with x to y carbon atom, and it is also called as " x-to y-carbon organic group ".

of the present invention containing sulfonate group multipolymer

ether-containing key monomer

Of the present inventionly must comprise structural unit (a) derived from one or more monomers (A) containing sulfonate group multipolymer, described monomer (A) is selected from the ether-containing key monomer represented by following formula (1) and (2).

In formula (1), R ₀represent hydrogen atom or CH ₃group, R represents CH ₂group, CH ₂cH ₂group or singly-bound, X represents the number (precondition is that then X represents the number of 1-5 if R is singly-bound) of 0-5, and R ₁for hydrogen atom or 1-to 20-carbon organic group,

In described formula, R _orepresent hydrogen atom or CH ₃group, R represents CH ₂group, CH ₂cH ₂group or singly-bound, X represents the number of 0-5, and R ₁for hydrogen atom or 1-to 20-carbon organic group.

In formula (1), owing to can obtain the multipolymer deposition rejection ability highly improved, R is preferably CH ₂cH ₂group.In (2), owing to can obtain the multipolymer deposition rejection ability highly improved, R is preferably CH ₂group.

As mentioned above, in formula (1) and (2), R ₁for hydrogen atom or 1-to 20-carbon organic group.R ₁be preferably 4-to 18-carbon organic group, and be more preferably 6-to 16-carbon organic group.R ₁functional group can be comprised, as amino, amide group, hydroxyl, alcohol oxygen groups, sulfonate group, carbonyl or carboxyl.R ₁ehter bond or sulfide linkage, ester bond or amido linkage can be comprised.Owing to can obtain the multipolymer deposition rejection ability highly improved, organic group is preferably alkyl, aryl and thiazolinyl.

Just suitable R ₁, what can specifically enumerate is that alkyl is as normal-butyl, isobutyl-, octyl group, lauryl, stearyl, cyclohexyl and 2-ethylhexyl; Thiazolinyl is as butylene, octenyl and nonene base; Aryl is as phenyl, styroyl, 2,3-or 2,4-xylyl, trimethylphenyl or naphthyl.

With regard to formula (1) monomer, suitable compound can be classified as by by the compound that following formula (3)-(7) represent.The compound represented by formula (3)-(7) is preferably by making vinyl carbinol or isoprene alcohol and corresponding 1) haloalkane, 2) epoxy compounds, 3) glycidyl compound, 4) ester cpds or 5) isocyanate compound reacts and obtains.

In formula (3)-(7), R ₀represent hydrogen atom or CH ₃group, identical with formula (1) of R with X, and R ₂represent 1-to 20-carbon alkyl, thiazolinyl or aryl.

With regard to formula (2) monomer, the compound represented can be classified as suitable compound by following formula (8) and (9).The compound represented by formula (8) and (9) is preferably by making glycidyl allyl ether and corresponding 1) alcohol or their alkylene oxide adducts or 2) amine or their alkylene oxide adduct react and obtain.

In formula (8) and (9), R ₀represent hydrogen atom or CH ₃group, identical with formula (2) of R with X, and R ₂and R ₃represent 1-to 20-carbon alkyl, thiazolinyl or aryl.

Even if show stable deposition rejection ability due to of the present invention in the basic conditions containing sulfonate group multipolymer, therefore monomer (A) does not preferably comprise ester group or amide group yet.

Above-mentioned component units (a) has the unsaturated double-bond (CH in wherein monomer (A) (i.e. above formula (1) or (2)) ₂=CH-) be singly-bound (-CH ₂-CH-) form.

Of the present inventionly must comprise structural unit (a) derived from one or more monomers (A) containing sulfonate group multipolymer, described monomer (A) is selected from the ether-containing key monomer represented by above formula (1) and (2), relative to all monomer derived structures of 100 quality %, but the ratio of described monomer (A) is 1 quality % or more is less than 49 quality %.In the present invention, monomer refers to the compound with unsaturated double-bond (referring to carbon-to-carbon double bond).If structural unit (a) is in above-mentioned scope, then obtain the multipolymer deposition rejection ability highly improved.But structural unit (a) is preferably 2 quality % or more relative to the ratio of all monomer derived structures of 100 quality % is less than 40 quality %, and more preferably 3 quality % or more are still less than 30 quality %.Comprise the structural unit (a) derived from monomer (A) in above-mentioned scope due to of the present invention containing sulfonate group multipolymer, therefore improve deposition rejection ability.

Owing to the structural unit (a) of relative hydrophobicity being incorporated into the present invention containing in sulfonate group multipolymer, therefore the described sulfonate group multipolymer that contains is by improving the interaction with tensio-active agent, inhibits the deposition of tensio-active agent.Because monomer (A) and monomer (B) and (C) even if also more easily interpolymerization occurs in hydrophilic solvent is as water, the deposition rejection ability that gained contains sulfonate group multipolymer therefore significantly can be improved.

carboxyl group-containing monomer

The structural unit (b) derived from carboxyl group-containing monomer (B) that must comprise specified proportion containing sulfonate group multipolymer of the present invention.

Carboxyl group-containing monomer of the present invention (B) to comprise 1) unsaturated double-bond and 2) monomer (belonging to the monomer of monomer (A) or monomer (C) not in monomer (B) scope) of carboxyl and/or its salt.What can specifically enumerate is that unsaturated monocarboxylic acid is as vinylformic acid, methacrylic acid, β-crotonic acid, Alpha-hydroxy vinylformic acid, Alpha-hydroxy methacrylic acid and these derivative and salt; Unsaturated dicarboxylic acid is as methylene-succinic acid, fumaric acid and toxilic acid and their salt.In the case, described unsaturated dicarboxylic acid monomer is only required to be in molecule the monomer comprising 1 unsaturated group and 2 carboxyls.Desirably toxilic acid, methylene-succinic acid, citraconic acid, fumaric acid etc. and their univalent metal salt, divalent metal salt, ammonium salt and organic ammonium salt (organic amine salt) etc. or their acid anhydrides.(methyl) acrylic ester monomer (A) can be the half amide of the half ester of unsaturated dicarboxylic acid monomer and 1-to 22-carbon alcohol, unsaturated dicarboxylic acid and 1-to 22-carbon amine, unsaturated dicarboxylic acid monomer and the half ester of 2-to 4-carbon glycol or the half amide of maleinamic acid and 2-to 4-carbon glycol.

The salt of unsaturated monocarboxylic acid and the salt of unsaturated dicarboxylic acid are metal-salt, ammonium salt or organic amine salt.In the case, with regard to metal-salt, specifiable is alkali-metal univalent metal salt, as sodium salt, lithium salts, sylvite, rubidium salt, cerium salt; The salt of alkaline-earth metal, as magnesium salts, calcium salt, strontium salt or barium salt; Aluminium salt or molysite.With regard to organic amine salt, specifiable organic amine salt is if alkanol amine salt is as monoethanolamine salt, diethanolamine salt or triethanolamine salt; Alkylamine salt is as an ethyl amine salt, diethyl amine salt or trismethylamine salt; Polyamines is as ethylenediamine salt or triethylenediamine salt.In these, because gained multipolymer deposition rejection ability height improves, therefore [described salt] preferably ammonium salt, sodium salt or sylvite.Sodium salt is preferred.

In carboxylic monomer (B), because gained multipolymer deposition rejection ability height improves, therefore preferred vinylformic acid, acrylate, toxilic acid and maleate.Vinylformic acid or acrylate are become must even be more preferably.

Carboxyl group-containing monomer (B) can be only one.But it can also be the structure derived from two or more.In the case, all structural units (b) derived from all carboxyl group-containing monomers (B) type comprising specified proportion containing sulfonate group multipolymer of the present invention.

Said structure unit (b) has the unsaturated double-bond (CH of wherein monomer (B) ₂=CH-) be singly-bound (-CH ₂-CH-) form.

Of the present inventionly must comprise structural unit (b) derived from carboxyl group-containing monomer (B) containing sulfonate group multipolymer, but its ratio is 50 quality % or more relative to all monomer derived structures of 100 quality % is less than 98 quality %.If structural unit (b) is in above-mentioned scope, then obtain the multipolymer deposition rejection ability highly improved.Relative to all monomer derived structures of 100 quality %, but the ratio of structural unit (b) is preferably 52 quality % or more is less than 97 quality %, and more preferably 55 quality % or more are still less than 95 quality %.

Due to the structural unit (b) comprising specified proportion containing sulfonate group multipolymer of the present invention, therefore when being used as detergent builder, the water solubility of described polymkeric substance becomes favourable, and [they] can reveal suppression effect to the deposition table with the interactional tensio-active agent of structural unit (a).

Calculate derived from the structural unit (b) of carboxyl group-containing monomer (B) by the present invention in mass ratio (the quality %) of all monomer derived structures time, calculate by corresponding acid.Such as, if it is the structural unit-CH of derived from propylene acid sodium ₂-CH (COONa)-, then mass ratio (quality %) is by respective acids, i.e. structural unit-the CH of derived from propylene acid ₂-CH (COOH) calculates.Similarly, when relative to all carboxyl group-containing monomers (B) calculated mass ratio (quality %), calculate by corresponding acid.

Such as, if it is sodium acrylate, then by corresponding acid, namely vinylformic acid carrys out calculated mass ratio (quality %).

When relative to all monomer derived structures, calculate derived from when being different from structural unit mass ratio (the quality %) containing acidic-group monomer of carboxyl group-containing monomer (B), calculate by corresponding acid.When relative to be different from carboxyl group-containing monomer (B) all containing acidic-group monomer calculated mass ratio (quality %) time, also calculate by corresponding acid.The quality of the structural unit that emulsion stability derives and emulsion stability calculates by unneutralized amine derived structure unit and unneutralized amine equally.Such as, with regard to vinyl-amine hydrochloride, mass ratio (quality %) calculates by corresponding non-neutralizing amine vinyl-amine.

containing sulfonate group monomer

Of the present invention containing sulfonate group multipolymer must comprise specified proportion derived from containing the structural unit (c) of sulfonate group monomer (C).

Of the present invention is to comprise 1 containing sulfonate group monomer (C)) one or more unsaturated double-bond (carbon-to-carbon double bond) and 2) monomer (but the monomer belonging to monomer (A) is not in monomer (C) scope) of one or more sulfonate group.

With regard to of the present invention containing with regard to sulfonate group monomer (C), what can specifically enumerate is vinyl sulfonic acid, styrene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, acrylamide-2-methyl propane sulfonic, 2-hydroxyl-3-allyloxy propanesulfonate, 2-hydroxy-3-methyl acryloxy propanesulfonate, isoprene sulfonic acid salt, sulfoethyl acrylate, sulfoethyl methacrylate, vinylformic acid sulphur propyl ester, methacrylic acid sulphur propyl ester, 2-hydroxyl-3-butylene sulfonic acid etc. and their salt.

Of the present invention above-mentioned containing in sulfonate group monomer (C), because resulting polymers characteristic stability is in time high, therefore preferably do not comprise ester group or amide group containing sulfonate group monomer, as styrene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, 2-hydroxyl-3-allyloxy propanesulfonic acid, 2-hydroxy-3-methyl allyloxy propanesulfonic acid, isoprene sulfonic acid and their salt.

Above-mentioned containing in sulfonate group monomer (C), the characteristic due to resulting polymers is optimum of the present invention, therefore most preferably 2-hydroxyl-3-allyloxy propanesulfonic acid and salt thereof.Namely the structure derived from 2-hydroxyl-3-allyloxy propanesulfonic acid or its salt is that most preferred the present invention is derived from the structural unit (c) containing sulfonate group monomer (C).

Salt containing sulfonate group monomer is metal-salt, ammonium salt or organic amine salt.In the case, with regard to metal-salt, specifiable is that monovalent base metal-salt is as sodium salt, lithium salts, sylvite, rubidium salt or cerium salt; The salt of alkaline-earth metal is as magnesium salts, calcium salt, strontium salt or barium salt; Aluminium salt or molysite.With regard to organic amine salt, specifiable organic amine salt is if alkanol amine salt is as monoethanolamine salt, diethanolamine salt or triethanolamine salt; Alkylamine salt is as an ethyl amine salt, diethyl amine salt or triethyl amine salt; Polyamines is as ethylenediamine salt or triethylenediamine salt.In these, because gained multipolymer deposition rejection ability height improves, therefore preferred ammonium salt, sodium salt and sylvite.Sodium salt is preferred.

The described sulfonate group monomer (C) that contains can be only one.But can be used two or more.In the present invention, a kind of structural unit (c) can be there is, or they can two or more form of mixtures exist.It is singly-bound (-CH containing the vinyl double bond in sulfonate group monomer (C) that said structure unit (c) has wherein corresponding ₂-CH-) form.

Relative to all monomer derived structures (structural unit (a), (b), (c) are always combined as 100 quality % with (d's)) of 100 quality %, but the sulfonate group multipolymer that contains of the present invention must comprise 1 quality % or more the structural unit (c) derived from monomer (C) being less than 49 quality %.If structural unit (c) is in above-mentioned scope, then obtain the multipolymer deposition rejection ability highly improved.Relative to all monomer derived structures of 100 quality %, but the ratio of structural unit (c) is preferably 2 quality % or more is less than 45 quality %, and more preferably 3 quality % or more are still less than 40 quality %.

Because they comprise the fact of the sulfonate group derived from repeating unit (c), contain sulfonate group multipolymer even if of the present invention under high rigidity condition, also can show the favourable improvement of dispersiveness or deposition rejection ability.Therefore, even if as during with residue bath water washing clothes under the clothes washing condition of harshness, the favourable improvement of deposition rejection ability also can be demonstrated.

other monomer

Of the present inventionly can comprise structural unit (d) derived from other monomer (D) containing sulfonate group multipolymer.

When of the present invention containing sulfonate group multipolymer comprise other monomer (D) time, other monomer (D) has no particular limits, as long as they can with above-mentioned monomer (A)-(C) copolymerization, and suitably to select according to desired effect.What can specifically enumerate is N-vinyl monomer, as NVP, N-vinyl formamide, N-vinyl acetamide, N-vinyl-N-methyl methane amide, N-vinyl-N-methylacetaniide or N-Yi Xi oxazolidinone; Amide monomer, as (methyl) acrylamide, N,N-DMAA or NIPA; Wherein 6 to 200 moles of ethylene oxide have added to the compound on hydroxyl unsaturated monomer, as 3-(methyl) allyloxy-1,2-dihydroxypropane, 3-allyloxy-1,2-dihydroxypropane, 3-allyloxy-1,2-dihydroxypropane, (methyl) vinyl carbinol or isoprene alcohol (as 3-allyloxy-1,2-bis-(gathering) oxygen Vinyl Ether propane); Allyl ether monomers is as (methyl) vinyl carbinol; Isoprene monomer is as isoprene alcohol; (methyl) alkyl acrylate monomer, as (methyl) butyl acrylate, (methyl) 2-EHA or (methyl) lauryl ester; (methyl) hydroxyalkyl acrylate monomer, as (methyl) Hydroxyethyl acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) hy-droxybutyl, (methyl) vinylformic acid 2-hydroxybutyl, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid alpha-hydroxymethyl ethyl ester, (methyl) vinylformic acid hydroxy pentane ester, (methyl) dihydroxypropyl peopentyl ester, the own ester of (methyl) vinylformic acid hydroxyl; Vinyl allyl monomer, as vinylbenzene, indenes or vinyl aniline, iso-butylene and vinyl-acetic ester.

Can be used alone a kind of above-mentioned other monomer (D), or they can two or more form of mixtures use.

With regard to of the present invention containing with regard to sulfonate group multipolymer, as long as said structure unit (a), (b) and (c) and structural unit (d) (if necessary) are introduced with the specified proportion described above, various structural unit can block form or random pattern existence.The present invention can suitably set containing the weight-average molecular weight of sulfonate group multipolymer, and has no particular limits.Concretely, the weight-average molecular weight containing sulfonate group multipolymer is preferably 2000-200, and 000, more preferably 3000-60,000, and most preferably 4000-30,000.If weight-average molecular weight is in above-mentioned scope, then deposits rejection ability and be tending towards improving.In this manual, weight-average molecular weight is the value recorded by GPC (gel permeation chromatography).With regard to concrete measuring method, [weight-average molecular weight] is calculated by the method described in application embodiment.

Due to except deposition rejection ability, of the present invention also have excellent antigelation characteristic containing sulfonate group multipolymer, even if therefore they at exacting terms as with residue bath water washing clothes or with under small volume of water washing clothes, also have excellent deposition rejection ability, therefore they are applicable in such as detergent composition.

of the present invention containing sulfonate group copolymer compositions (polymer composition)

The sulfonate group copolymer compositions that contains of the present invention must comprise of the present invention containing sulfonate group multipolymer.The component be different from containing sulfonate group multipolymer is optional.Usually, [described composition] also comprises one or more and is selected from following those: polymerization starter remnants, residual monomer, polyreaction by product and water.Suitable form containing sulfonate group copolymer compositions comprises the form of 30-80 quality % containing sulfonate group multipolymer and 20-70 quality % water.

of the present invention containing sulfonate group multipolymer preparation method

With regard to of the present invention containing with regard to sulfonate group multipolymer preparation method, except as otherwise noted, identical with the polymerisation process known or through improving method can be used.With regard to can obtain the present invention containing sulfonate group multipolymer method with regard to, obtain [they] by making the monomer component copolymerization comprising ether-containing key monomer (A), carboxyl group-containing monomer (B) and contain sulfonate group monomer (C) as required component.When making monomer component copolymerization, above-mentioned other monomer (D) also can copolymerization when needed.

In this type of preparation method, polymerization starter is used to make monomer component copolymerization.The monomer type comprised in suitable setting monomer component and consumption, make to form structural unit containing sulfonate group multipolymer with above-mentioned those are identical.In other words, the proportion of composing forming the above-mentioned various monomers containing sulfonate group multipolymer be 1 quality % or more but be less than 49 quality % above-mentioned ether-containing key monomer (A), 50 quality % or more but be less than 98 quality % carboxyl group-containing monomer (B) and 1 quality % or more but be less than 49 quality % containing sulfonate group monomer (C).As mentioned above, also can use above-mentioned other monomer (D) with these copolymerization, when monomer (A) to (C) adds up to 100 quality %, its amount is 0-10 quality %.More preferably 2 quality % or more but be less than 40 quality % ether-containing key monomer (A), 52 quality % or more but be less than 97 quality % carboxyl group-containing monomer (B) and 2 quality % or more but be less than 45 quality % containing sulfonate group monomer (C).Even more preferably 3 quality % or more but be less than 30 quality % ether-containing key monomer (A), 55 quality % or more but be less than 95 quality % carboxyl group-containing monomer (B) and 3 quality % or more but be less than 40 quality % containing sulfonate group monomer (C).The total amount of above-mentioned monomer (A), (B), (C) and (D) is 100 quality %.

In the present invention, with regard to the copolyreaction of monomer (A)-(C) and other monomer (D) (if necessary), preferred use water is as the solvent of 50 quality % or more, and/or described copolyreaction is preferably implemented under the existence of chain-transfer agent.More preferably use water as the solvent of 50 quality % or more, and described copolyreaction is more preferably implemented under the existence of chain-transfer agent.In the case, by using water as the solvent of 50 quality % or more, organic solvent amount used in polyreaction can keep low-level, therefore has the advantage of effectively obtained lower molecular weight containing sulfonate group multipolymer.Especially, when sulfurous acid or sulphite are used as chain-transfer agent, quantitatively can introduce sulfonate group at gained containing sulfonate group multipolymer end as mentioned below, and antigelation characteristic is improved further.

Therefore, the suitable embodiments of preparation method of the present invention relate to comprise following operation containing sulfonate group multipolymer preparation method: use water as the solvent for use of 50 quality % or more and usage chain transfer agent, implement formula (1) or (2) ether-containing key monomer (A) that 1 quality % or more is still less than 50 quality %, 50 quality % or more are still less than the carboxyl group-containing monomer (B) of 98 quality %, 1 quality % or more but be less than the polyreaction containing sulfonate group monomer (C) and other monomer (D) (if necessary) of 50 quality % (precondition be monomer (A), (B), (C) and the percent of total of (D) be 100 quality %).

Have no particular limits for the solvent in above-mentioned embodiment, as long as it comprises the water of solvent for use total amount 50 % by weight or more ratio.From the monomer solubleness angle in a solvent improved for polyreaction, organic solvent can be added when needed.In the case, the water-content in total mixed solvent is still 50 % by weight or more.Just can be used for regard to organic solvent in the case, specifiable is that lower alcohol is as methyl alcohol, ethanol or Virahol; Lower ketones is as acetone, methyl ethyl ketone or metacetone; Ether is as dimethyl ether or dioxane; Acid amides is as dimethylformaldehyde.These solvents can be used alone, or can two or more form of mixtures use.In the present invention, relative to solvent for use total amount, the amount of water is preferably 80 % by weight or more.Most preferably only use water (namely 100 % by weight).

In the preparation process in accordance with the present invention, preferred condition implements copolyreaction under the existence of chain-transfer agent.The chain-transfer agent that can be used in the case has no particular limits, as long as they are compounds of tunable molecular weight, and can use the chain-transfer agent known.What can specifically enumerate is that amine-thiol chain transfer agents is as mercaptoethanol, thioglycerol, mercaptoethanol acid, 2 mercaptopropionic acid ester, 3-mercaptopropionic acid ester, mercaptosuccinic acid, the misery ester of thioglycol, 3-thiohydracrylic acid monooctyl ester, mistabrom, n-dodecyl mereaptan, spicy thioalcohol or thioglycol acid butyl ester; Halogenide is as tetracol phenixin, methylene dichloride, bromofom or three chloro-bromothanes; Secondary alcohol is as Virahol or glycerine; Suboxide is as phosphorous acid, Hypophosporous Acid, 50 and their salt (sodium hypophosphite, potassium hypophosphite etc.) or sulfurous acid, hydrosulphite, dithionic acid, the inclined sulfurous acid of acid and their salt (sodium bisulfite, Potassium hydrogen sulfite, sodium hyposulfate, potassium hyposulfate, sodium metabisulfite, partially Potassium hydrogen sulfite etc.).Above-mentioned chain-transfer agent can be used alone, or uses with the form of mixtures of two or more.In these, it is desirable to use sulfurous acid and sulphite in copolyreaction of the present invention.Thus, quantitatively can introduce sulfonate group at gained containing sulfonate group copolymer chain end, and antigelation characteristic can be improved.Can quantitatively introduce sulfonate group to show, sulphite is very effective as chain-transfer agent, therefore without the need to adding excessive chain-transfer agent etc. in polymerization reaction system.Not only increase the reduction of multipolymer preparation cost, but also improve preparation efficiency.Impurity can also be reduced comprehensively.By sulphite is joined in polymerization reaction system, needed for control resulting polymers molecular weight increases above.

In above-mentioned preparation method, comprise sulfurous acid and/or sulphite (hereafter writes a Chinese character in simplified form into " sulfurous acid (salt) " as chain-transfer agent as above.Except sulfurous acid (salt), also in above-mentioned preparation method, use initiator.Heavy metal ion also can be used as reaction promotor.

Above-mentioned sulfurous acid (salt) refers to sulfurous acid or acidic sulfurous acid or their salt.Its sulfite/acidic sulfurous acid is the form of salt is suitable.When sulfurous acid/acidic sulfurous acid is salt, except above-mentioned example, atoms metal, ammonium or organic ammonium salt are also suitable.With regard to above-mentioned atoms metal, desirably such as following salt: basic metal monovalent metal atom is as lithium, sodium or potassium; Alkaline-earth metal divalent metal atom is as calcium or magnesium; Or trivalent metal atom is as aluminium or iron.With regard to organic ammonium (organic amine), desirably alkanolamine is as thanomin, diethanolamine and trolamine and triethylamine.It can also be ammonium.Therefore, as the sulphite be applicable in the present invention, specifiable is such as sodium bisulfite, Potassium hydrogen sulfite, ammonium bisulfite, S-WAT, potassium sulfite and ammonium sulphite.Especially desirably sodium bisulfite.Above-mentioned sulfurous acid (salt) can be used alone, or uses with the form of mixtures of two or more.

In the method for the invention, the add-on of chain-transfer agent has no particular limits, if it be conducive to monomer (A), amount that (B), (C) and other monomer (D) (if necessary) are polymerized.Relative to all monomer components of 1 mole of monomer (A), (B), (C) and monomer (D) (if necessary), it is preferably 1 to 20g, more preferably 2 to 15g.If it is less than 1g, then there is the risk of uncontrollable molecular weight.On the contrary, if it is more than 20g, then form a large amount of impurity, and there is the risk of polymer purity reduction.Especially when using sulphite, excessive sulphite decomposes in reaction system, and there is the risk producing sulphurous acid gas.In addition, also there is the risk that [excessive chain-transfer agent] causes economic loss.

With regard to above-mentioned initiator, those that know can be used.Such as, desirably hydrogen peroxide; Persulphate is as Sodium Persulfate, Potassium Persulphate or ammonium persulphate; Azo-compound (2-amidine propane) hydrochloride as two in 2,2'-azo, 4,4'-azos two (4-cyanopentanoic acid), Diisopropyl azodicarboxylate or 2,2'-azo two (4-methoxyl group-2,4-methyl pentane nitrile); Organo-peroxide is as benzoyl peroxide, lauroyl peroxide, peracetic acid, ditertiary butyl peroxide or hydrogen phosphide cumene.In these polymerization starters, preferred hydrogen peroxide and persulphate, and most preferably persulphate.These polymerization starters can be used alone, or use with the form of mixtures of two or more.

The consumption of initiator has no particular limits, if it be can trigger monomer (A), (B), (C) and other monomer (D) (if necessary) the amount of copolyreaction.But comprise all monomer components of monomer (A), (B), (C) and other monomer (D) (if necessary) relative to 1 mole, it is preferably less than 10g, more preferably 1-5g.

The heavy metal ion that can be used as reaction promotor in the present invention refers to that proportion is 4g/cm ³or higher metal.With regard to above-mentioned metal ion, desirably such as iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, ruthenium etc.One, two or more these metals can be used.Wherein, more preferably iron.The ionic valence of above-mentioned heavy metal ion has no particular limits.Such as, when iron is used as heavy metal, the iron ion in initiator can be Fe ²⁺or Fe ³⁺, or these combination.

Above-mentioned heavy metal ion has no particular limits, as long as it comprises in the form of an ion.Due to the tractability of excellence, the method for the solution that use is dissolved heavy metal compound and obtained is favourable.Be comprise those that expect to be contained in heavy metal ion in initiator for heavy metal compound in the case, and can determine according to initiator used.When using iron as above-mentioned heavy metal ion, use heavy metal compound as Mohr's salt (Fe (NH ₄) ₂(SO ₄) ₂-6H ₂o), ferrous sulfate, iron protochloride or iron(ic) chloride are suitable.When using manganese as heavy metal ion, Manganous chloride tetrahydrate can be used aptly.When using these heavy metal compounds, they can use as an aqueous solution, this is because they are all water-soluble cpds and tractability is good.Dissolve above-mentioned heavy metal compound and the solvent of solution that obtains is not limited to water, and only need to be in the present invention is containing the preparation of sulfonate group multipolymer, does not hinder polyreaction and dissolves those of heavy metal compound.

With regard to the amount of heavy metal ion, when using above-mentioned heavy metal ion, in polymerisation process of the present invention, comprise catalytic amount is suitable.In this manual, catalytic amount is used as catalyzer but the amount be not incorporated in ultimate aim product.Concretely, it is 100ppm or lower, preferred 10ppm or lower, and more preferably 5ppm or lower.

With regard to above-mentioned heavy metal ion content, the total mass of polymeric reaction solution when completing relative to polyreaction, it is preferably 0.1-10ppm.If the content of heavy metal ion is less than 0.1ppm, then there is the risk that cannot manifest the abundant effect of heavy metal ion.On the other hand, if heavy metal ion content is more than 10ppm, then there is the risk causing resulting polymers color to be deteriorated.If heavy metal ion content is high, then exist when resulting polymer is used as detergent builder, it will cause the risk of detergent builder fouling.

Refer to that the polyreaction in polymeric reaction solution substantially completes and obtains the time point of desired polymkeric substance above when polyreaction completes.Such as, when with the polymkeric substance be polymerized in basic cpd and in polymeric reaction solution, according in and the total mass of post-polymerization solution calculate heavy metal ion content.When comprising two or more heavy metal ion, the total amount of heavy metal ion should in above-mentioned scope.

With regard to the combination of above-mentioned initiator and chain-transfer agent, most preferably use persulphate and sulphite all kinds of in one or more.In the case, the mixture ratio of persulphate and sulphite has no particular limits, but relative to 1 mass parts persulphate, is suitable for using 0.5-5 mass parts sulphite.Relative to 1 mass parts persulphate, the lower limit of sulphite is more preferably 1 mass parts, and most preferably is 2 mass parts.Relative to 1 mass parts persulphate, the upper limit of sulphite is more preferably 4 mass parts, and most preferably is 3 mass parts.Herein, if sulphite is less than 0.5 mass parts, then there is the risk that when reducing initiator total amount, molecular weight will increase.On the contrary, when it is more than 5 mass parts, then there is side reaction increase thus the risk of impurity increase.

The combination of above-mentioned chain-transfer agent, initiator and reaction promotor has no particular limits, and can suitably select from each example above-mentioned.Such as, with regard to the combination of chain-transfer agent, initiator and reaction promotor, suitable form is as sodium bisulfite (SBS)/hydrogen peroxide (H ₂o ₂), sodium bisulfite (SBS)/Sodium Persulfate (NaPS), sodium bisulfite (SBS)/Fe, sodium bisulfite (SBS)/hydrogen peroxide (H ₂o ₂)/Fe, sodium bisulfite (SBS)/Sodium Persulfate (NaPS)/Fe, sodium bisulfite (SBS)/Sodium Persulfate (NaPS)/hydrogen peroxide (H ₂o ₂) and sodium bisulfite (SBS)/oxygen/Fe.More preferably sodium bisulfite (SBS)/Sodium Persulfate (NaPS), and sodium bisulfite (SBS)/Sodium Persulfate (NaPS)/Fe.Most preferably sodium bisulfite (SBS)/Sodium Persulfate (NaPS)/Fe.

Comprise all monomer components of monomer (A), (B), (C) and other monomer (D) (if necessary) relative to 1 mole, the total amount of above-mentioned chain-transfer agent used, initiator and reaction promotor is preferably 2-20g.Adopt within the scope of this, effectively can obtain of the present invention containing sulfonate group multipolymer, and the molecular weight distribution containing sulfonate group multipolymer can be controlled on demand.More preferably 4-18g, and even more preferably 6-15g.

Just above-mentioned polymerization starter and chain-transfer agent are joined with regard to the method in reaction vessel, continuous Adding Way can be adopted as dripped or add in batches.Also chain-transfer agent can be introduced separately in reaction vessel, and can be blended with various monomers (A)-(C) or other monomer (D) that form monomer component in advance, or blended with solvent.

Just in above-mentioned copolyreaction method, monomer component and polymerization starter are joined with regard to the method in reaction vessel, following method is suitable: in reaction vessel, add all monomer components, and implements the method for copolyreaction by adding polymerization starter in reaction vessel; In reaction vessel, add a part of monomer component, and add the method for polymerization starter and residual monomer component enforcement copolyreaction by continuous in reaction vessel or substep (preferably continuous); In reaction vessel, add polymerization solvent and add the method for all monomer components and polymerization starter; The part of a kind of [such as monomer (B)] in monomer (A)-(C) is added in reaction vessel, and by method of adding polymerization starter and residual monomer component (remaining monomer (B) and all monomers (A), (C) and monomer (D) (if necessary)) enforcement copolyreaction to (preferably continuous) in reaction vessel etc.In these class methods, preferably polymerization starter and monomer component are added drop-wise in reaction vessel continuously to implement the method for copolyreaction, because the molecular weight of copolymer distribution of narrow (sharply) can be obtained, and when being used as detergent builder, can improve dispersiveness.

With regard to above-mentioned copolyreaction method, the method for such as conventional use can be used as solution polymerization, mass polymerization, suspension polymerization and letex polymerization, and have no particular limits.But preferred solution is polymerized.With regard to the solvent for this method, preferably wherein total solvent 50 quality % as above is the mixed solvent of water, or water itself.Water itself is used to be desirable, because can removal step be saved.

Above-mentioned copolyreaction method can intermittent mode or continuous mode enforcement.During with regard to needing during copolyreaction can solvent with regard to, those that know can be used.Desirably water; Alcohol is as methyl alcohol, ethanol and Virahol; Glycerine; Polyoxyethylene glycol; Aromatics or aliphatic hydrocrbon are as benzene,toluene,xylene, hexanaphthene or normal heptane; Ester is as ethyl acetate; Ketone is as acetone or methyl ethyl ketone; Acid amides is as dimethyl formamide; Ether is as ether or dioxane.These can be used alone, or use two or more simultaneously.Wherein, from the solubleness angle of monomer component and gained multipolymer, be suitable for using water and a kind of, two or more solvents, described solvent is selected from by the following group formed: 1-to 4-carbon lower alcohol.

With regard to the amount of above-mentioned solvent for use, relative to the monomer component of 100 quality %, 40-200 quality % is suitable.More preferably 45 quality % or more, and even more preferably 50 quality % or more.More preferably 180 quality % or less, and even more preferably 150 quality % or less.If solvent for use amount is less than 40 quality %, then there is the risk that gained molecular weight of copolymer increases.If it is more than 200 quality %, then there is gained copolymer concentration will reduce, and solvent removal will become required risk.When polyreaction starts, a part or all solvents are joined in reaction vessel.During polyreaction, a part of solvent can be added (dropping) in reaction system, or can during polyreaction, by being dissolved in described solvent in advance by monomer component and initiator, described solvent is added together with these components (dropping) in reaction system.

In above-mentioned copolyreaction method, according to copolyreaction method, solvent and initiator used, suitably determine that copolyreaction condition is as copolyreaction temperature.But with regard to copolyreaction temperature, in general 0 DEG C and higher be suitable, and 150 DEG C or lower is suitable.More preferably 40 DEG C or higher, even more preferably 60 DEG C or higher, and especially preferably 80 DEG C or higher.More preferably 120 DEG C or lower.Even more preferably 110 DEG C or lower.Specifically, when using sulfurous acid (salt), copolyreaction temperature is generally 60 DEG C to 95 DEG C, preferably 70 DEG C to 95 DEG C, and more preferably 80 DEG C to 95 DEG C.In the case, be less than 60 DEG C and then there is generation in a large number derived from the risk of the impurity of sulfurous acid (salt).On the contrary, if it is more than 95 DEG C, then there is the risk discharging poisonous sulphurous acid gas.

In polyreaction, above-mentioned copolyreaction temperature is not always must keep substantially constant.Such as, polyreaction can at room temperature cause, raised temperature within the suitable temperature rising stage, or to the temperature of setting, keeps set temperature with suitably temperature rate-of-rise raised temperature subsequently.According to the dropping method of monomer component and initiator, also can make temperature during polyreaction in float (rise or decline) in time.

With regard to the above-mentioned copolyreaction time, 30-300min is suitable.More preferably 60-240min, and even more preferably 120-180min.

Pressure in reaction system in above-mentioned copolyreaction method can be standard pressure (normal atmosphere), low pressure or high pressure.But with regard to gained molecular weight of copolymer, preferably implement under standard pressure, or confined reaction system and under high pressure implementing.Slave unit, as pressurizing device or reliever and pressure-resistant reaction vessel and pipeline system angle are seen, is preferably implemented under standard pressure (normal atmosphere).Atmosphere in reaction system can be air atmosphere.But be preferably inert atmosphere.Such as, it is favourable for system being taken a breath as nitrogen with rare gas element before polyreaction causes.

In above-mentioned copolyreaction, the pH during preferably making polyreaction is for acid.When using persulphate and hydrosulphite as above-mentioned initiator especially at the same time, preferably implement in acid condition.By implementing in acid condition, the control that polymerization reaction system solution viscosity is raised can be kept, and advantageously can obtain described multipolymer.Carry out under a high concentration condition due to polyreaction can be made, therefore can significantly improve preparation efficiency, [described polyreaction] can become high density polyreaction, and wherein the ultimate density of solid is 40% or higher, and the product that residual monomer total content is 30,000ppm or lower can be obtained.Also can improve the polymerizability containing sulfonate group monomer.

With regard to above-mentioned acidic conditions, the pH during polyreaction at reaction soln 25 DEG C is preferably 1 to 6.It is more preferably 5 or lower, and is even more preferably 3 or lower.The multipolymer obtained by above-mentioned copolyreaction method in statu quo can be used as the main ingredient (detergent builder) in detergent composition.But when needed, their neutralize and use by alkali material.With regard to alkaline matter, be suitable for using inorganic salt as the oxyhydroxide of monovalent metal or divalent metal, muriate or carbonate; Ammonia; Organic ammonium (organic amine) etc.

Suitably can change according to initiator with speed in during enforcement copolyreaction.Such as, when to use persulphate and hydrosulphite simultaneously, implement the copolyreaction of monomer component, wherein when above-mentioned monomer can salify time, monomer neutralization ratio is suitably 0-60 quality %.When the total molar percentage number of the monomer with carboxyl and/or sulfonate group is 100 % by mole, be the monomer molar % of salify with rate representation in monomer.If in monomer and speed more than 60 % by mole, then the polymerization rate in polymerization process does not improve, and exist gained molecular weight of copolymer reduce or production efficiency reduce risk.It is more preferably 50 % by mole or lower, and even more preferably 40 % by mole or lower.It is especially preferably 30 % by mole or lower, and is more preferably 20 % by mole or lower.Most preferably 10 % by mole or lower.

Be with regard to the copolyreaction implementation method of 0-60 % by mole with regard to wherein above-mentioned monomer neutralization ratio, suitable method is such as, when monomer is unsaturated carboxylic acid monomer, make to be the method that acid unsaturated carboxylic acid monomer does not neutralize experience copolyreaction, maybe when use alkaline matter unsaturated carboxylic acid monomer is neutralized into salt form as sodium salt or ammonium salt time, make neutralization ratio be 0-60 % by mole those experience copolyreaction method.

The above-mentioned sulfonate group multipolymer (or polymer composition) that contains can be used as water conditioner, fibre finish, dispersion agent, detergent builder (or detergent composition), scale inhibitor (Scale inhibitors), metal ion encapsulant, thickening material, various tackiness agent, emulsifying agent, skin-protecting agent, hair nursing agent etc.As detergent builder, they can join and be applied in the washing composition of various uses, as clothes washing, dish washing, household washing, hair wash, take a shower, brush teeth, car cleaning etc.

the laundry detergent of described multipolymer and cleaning compositions purposes

The sulfonate group multipolymer (or polymer composition) that contains of the present invention can join in detergent composition.

The described sulfonate group multipolymer content in detergent compositions that contains has no particular limits.But from the excellent properties angle manifested as washing assistant, relative to the total amount of detergent composition, the content containing sulfonate group multipolymer is preferably 0.1-20 quality %.More preferably 0.3-15 quality %, and even more preferably 0.5-10 quality %.

In the laundry detergent that multipolymer of the present invention can be used for comprising surfactant system or cleaning compositions, described surfactant system comprises C ₁₀-C ₁₅alkylbenzene sulfonate (LAS) and one or more cosurfactants, described cosurfactant is selected from nonionic, positively charged ion, anionic cosurfactant, or their mixture.The selection of cosurfactant can be determined by required beneficial effect.In one embodiment, described cosurfactant is chosen as nonionogenic tenside, preferred C ₁₂-C ₁₈alkylethoxylate.In another embodiment, described cosurfactant is chosen as anion surfactant, preferred C ₁₀-C ₁₈alkyl alkoxy sulfate (AE _xs), wherein x is 1 to 30.In another embodiment, described cosurfactant is chosen as cats product, preferred dimethyl hydroxy ethyl lauryl ammonium chloride.If described surfactant system comprises C ₁₀-C ₁₅alkylbenzene sulfonate (LAS), then the consumption of LAS is by weight of the composition about 9% to about 25%, or about 13% to about 25%, or in the scope of about 15% to about 23%.

Above-mentioned laundry detergent or cleaning compositions preferably comprise the copolymer compositions comprising hydrophobic group of about 1 % by weight to about 20 % by weight.

Described surfactant system also comprises by weight of the composition 0% to about 7%, or about 0.1% to about 5%, or the cosurfactant of about 1% to about 4%, described cosurfactant is selected from nonionic cosurfactant, positively charged ion cosurfactant, anionic cosurfactant and their mixture.

The limiting examples of nonionic cosurfactant comprises: C ₁₂-C ₁₈alkylethoxylate, as purchased from Shell nonionogenic tenside; C ₆-C ₁₂alkyl phenolic alkoxy thing, wherein alcoxylates unit is the mixture of vinyloxy group and propyleneoxy units; C ₁₂-C ₁₈alcohol and C ₆-C ₁₂the condenses of alkylphenol and ethylene oxide/propylene oxide block alkyl polyamine ethoxylate, such as, derive from BASF's as US6,150, the C discussed in 322 ₁₄-C ₂₂mid-chain branched alcohol BA; As US6,153,577, US6,020,303 and US6,093, the C discussed in 856 ₁₄-C ₂₂mid-chain branched alkyl alkoxylates BAE _x, wherein x is 1-30; As the U.S.4 of the Llenado that on January 26th, 1986 announces, 565, the alkyl polysaccharide discussed in 647; Specifically, as US4,483,780 and US4,483, the alkyl polyglycoside discussed in 779; As US5,332, the polyhydroxy fatty acid amide discussed in 528; And as US6,482,994 and WO01/42408 in ether capped poly-(alkoxylate) alcohol tensio-active agent of discussing.

The limiting examples of Semi-polar nonionic cosurfactant comprises: water-soluble amine oxides, its comprise a moieties with about 10 to about 18 carbon atoms and 2 be selected from by the part of the following group formed: the moieties and the hydroxyalkyl moiety that comprise about 1 to about 3 carbon atom; Water soluble oxidized phosphine, its comprise 1 moieties with about 10 to about 18 carbon atoms and 2 be selected from by the part of the following group formed: the moieties and the hydroxyalkyl moiety that comprise about 1 to about 3 carbon atom; And water soluble sulfoxide, described water soluble sulfoxide comprise a moieties with about 10 to about 18 carbon atoms and one be selected from by the part of the following group formed: moieties and the hydroxyalkyl moiety with about 1 to about 3 carbon atom.See WO01/32816, US4,681,704 and US4,133,779.

The non-limiting example of positively charged ion cosurfactant comprises: the quaternary ammonium surfactant can with maximum 26 carbon atoms, and it comprises: as US6, and 136, alkoxy quaternary ammonium (AQA) tensio-active agent described in 769; As 6,004, the dimethyl hydroxy ethyl quaternary ammonium described in 922; Dimethyl hydroxy ethyl lauryl ammonium chloride; Polyamine cationic tensio-active agent as described in WO98/35002, WO98/35003, WO98/35004, WO98/35005 and WO98/35006; As U.S. Patent No. 4,228,042,4,239,660,4,260,529 and US6,022, the cationic ester surfactant described in 844; With such as US6,221,825 and the amino surfactants described in WO00/47708, in particular to cocoamidopropyl dimethyl amine (APA).

The limiting examples that can be used for anionic cosurfactant herein comprises: C ₁₀-C ₂₀the primary, side chain and random alkyl-sulphate (AS); C ₁₀-C ₁₈secondary (2,3) alkyl-sulphate; C ₁₀-C ₁₈alkyl alkoxy sulfate (AE _xs), wherein x is 1-30; Comprise/comprise the C of 1-5 ethoxy unit ₁₀-C ₁₈alkyl alkoxy carboxylates; As US6,020,303 and US6,060, the alkyl-sulphate of the mid-chain branched described in 443; As US6,008,181 and US6,020, the alkyl alkoxy sulfate of the mid-chain branched described in 303; Modified alkylbenzene sulfonates (MLAS) as described in WO99/05243, WO99/05242 and WO99/05244; Methyl ester sulfonate (MES); With sulfonated α-olefin (AOS).

The invention still further relates to the composition comprising multipolymer of the present invention and surfactant system, described surfactant system comprises C ₈-C ₁₈linear alkyl benzene sulphonic acid tensio-active agent and cosurfactant.Described composition can be any form, namely, form can be liquid, solid is (as powder, particle, agglomerate, paste, tablet, pouch, bar, gel), emulsion, with the type that two Compartment comtainer is sent, spraying or foam shampoo, the cleaning piece of pre-wet (namely, the cleaning compositions combined with nonwoven material, the US6 of the people such as such as Mackey, 121, that described in 165), the dry wipe activated by human consumer's use water (namely, the cleaning compositions combined with nonwoven material, the US5 of the people such as such as Fowler, 980, that described in 931), and other homogeneous phase or heterogeneous consumer cleaning product's form.

In one embodiment, cleaning compositions of the present invention is liquid or solid laundry detergent composition.In another embodiment, cleaning compositions of the present invention is hard surface cleaning composition, and preferably wherein said hard surface cleaning composition soaks into matrix of nonwoven filament.As used herein, " soaking into " refers to that described hard surface cleaning composition is placed in and contacts with nonwoven substrate, and described hard surface cleaning composition is infiltrated at least partially in described nonwoven substrate.Preferably, described hard surface cleaning composition is by saturated for described nonwoven material.Described cleaning compositions also can be used in car care composition, for clean various surface as hardwood, ceramic tile, pottery, plastics, leather, metal, glass.This cleaning compositions also can be designed for personal care and pet nursing composition as shampoo Compositions, bath shampoo, liquid or solid soap and other cleaning compositions (wherein, tensio-active agent can contact with free hardness ions) in, and need in the composition of hardness tolerant surfactant system, as oil drilling compositions for all.

In another embodiment, described cleaning compositions is dish cleaning composition, as the automatic platter washing composition of liquid hand platter washing composition, the automatic platter washing composition of solid, the automatic platter washing composition of liquid and tablet/unit dosage.

Automatic detergent composition can comprise low whipability nonionogenic tenside (LFNI).The content of LFNI is about 0.25% to about 4%.Because they give the drying effect (especially from glass) through improving of gel automatic detergent, LFNI is generally used in automatic detergent most.Preferred LFNI comprises Nonionic alkoxylated tensio-active agent, especially derived from the ethoxylate of primary alconol, and the blend of itself and more complicated tensio-active agent block polymer as trans in polyoxypropylene/polyoxyethylene/polyoxypropylene.PO/EO/PO polymeric surfactant is well known, has and presses down bubble or froth breaking effect, when especially relating to common food soil composition as egg.In a preferred embodiment, LFNI is ethoxylated surfactant, and it is derived from the reaction of the MHA or alkylphenol and the average every mol of alcohol of about 6 to about 15 moles of ethylene oxide or alkylphenol that comprise about 8 to about 20 carbon atoms except ring carbon atom.Especially preferred LFNI is derived from the straight-chain fatty alcohol (C comprising about 16 to about 20 carbon atoms ₁₆-C ₂₀alcohol), preferred C ₁₈the condensation of alcohol with average about 6 to about 15 moles, preferably about 7 to about 12 moles and the most preferably from about every mol of alcohol of 7 to about 9 moles of ethylene oxide.Relative on average, so derivative ethoxylated non-ionic surface active agent preferably has the distribution of narrow oxyethyl group.

LFNI optionally can comprise the propylene oxide of content maximum about 15 % by weight.BASF-WyandotteCorp. (Wyandotte, Mich) called after with some block polymer surfactant compound be applicable in gel automatic detergent of the present invention.Also spendable LFNI comprise can trade(brand)name " SLF-18Poly-tergent " from the commercially available many ethoxylates of C-18 alcohol with the ethoxylation degree of about 8 of BASFCorp.

Platter washing composition also can comprise polymer dispersant, its content by the weighing scale of described washing composition usually 0 to about 25%, preferably about 0.5% to about 20%, more preferably from about in 1% to about 7% scope.Described polymer dispersant can be U.S. Patent No. 4, and 659, the ethoxylated cationic diamines described in 802 or ethoxylated cationic polyamines.Other polymer dispersant be suitable for comprises by the multipolymer of vinylformic acid, toxilic acid and methacrylic acid synthesis as provided by Rohm & Haas 480N, and with acrylic acid-maleic acid (ratio is for 80/20) the phosphono end group dispersion agent multipolymer deriving from Rohm & Haas that trade(brand)name Acusol425N (E) sells.The polymkeric substance comprising carboxylate salt and sulfonate monomer as polymkeric substance (being provided by Alco) is also acceptable polymer dispersant.In one embodiment, with trade(brand)name 725 sales polymkeric substance has the vinylbenzene of having structure and acrylic acid multipolymer:

X:y=60:40 or 50:50, MW=8000.

725 also can provide the beneficial effect suppressing metallic corrosion.

Other polymer dispersant is low-molecular-weight modified polyacrylate multipolymer, comprises U.S. Patent No. 4,530,766 and 5,084,535 and December 15 nineteen eighty-two announce european patent application No.66, the low-molecular weight copolymer of the carboxylic acid of unsaturated aliphatic disclosed in 915.

Platter washing composition can use detergent builder to help regulate mineral substance hardness and dispersity.Inorganic and organic washing-assisting detergent can be used.The group of the following composition of the optional freedom of embodiment of this type of dish cleaning product: phosphoric acid salt, oligomeric phosphate salts or its polymkeric substance and salt, silicate oligomer or its polymkeric substance and salt, silico-aluminate, pure aluminium silicate magnesium salts, Citrate trianion, MDGA and/or its salt, glutamic acid diacetic acid and/or its salt and their mixture.Phosphoric acid salt detergent builder include but not limited to an alkali metal salt of Tripyrophosphoric acid, ammonium salt and alkanol ammonium salts.Silicate-like builder herein to a certain degree to dissolve any silicate making them can not adversely affect gel detergent compositions spotting/film forming characteristics.Aluminosilicate builder materials can be used in the present composition, but is not preferred for inventory dishwashing and washs in washing composition.Carbonate builders comprises the German Patent No.2 as announced on November 15th, 1973, and 321, alkaline-earth metal disclosed in 001 and alkaline carbonate.Can use sodium carbonate and the concentrated crystal soda of various grade and type, wherein some especially can be used as the carrier of other composition especially detersive surfactant.Organic detergent builders comprises multiple polycarboxylic acid salt compound.Other available washing assistant comprises ether hydroxyl polycarboxylic acid salt, the multipolymer of maleic anhydride and ethene or vinyl methyl ether, phloroglucinol-2,4,6-trisulfonic acid and carboxymethyl succinic acid, polynary acetic acid is as the multiple an alkali metal salt of ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA), ammonium salt and substituted ammonium salt, and polycarboxylate is as mellitic acid, succsinic acid, oxygen di-succsinic acid, More Malay acid, benzene-1,3,5-tricarboxylic acid, carboxymethyl succinic acid and their resolvability salt.Because Citrate builders such as citric acid and soluble salt thereof (especially sodium salt) can derive from renewable resources and due to their biodegradability, therefore they are for the polycarboxylate washing assistant be even more important in heavy duty type laundry detergent and inventory dish detergent compositions.MDGA and/or its salt (MGDA) also can be used as the washing assistant in the present composition.Preferred MGDA compound is the salt of MDGA.Suitable salt comprises di-ammonium salts, di-potassium and preferred disodium salt.Glutamic acid diacetic acid and/or its salt (GLDA) also can be used as the washing assistant in the present composition.Preferred GLDA compound is the salt of glutamic acid diacetic acid.Suitable salt comprises di-ammonium salts, di-potassium and preferred disodium salt.L-hydroxy ethylene-l, l-di 2 ethylhexyl phosphonic acid (HEDP) also can be used as the washing assistant in the present composition.

Spices can be joined in composition of the present invention.Described detergent composition can comprise the reagent effectively as corrosion inhibitor and/or antirust auxiliary agent.

As used herein, " detergent enzyme " refers in gel detergent compositions any enzyme with clean, decontamination or other beneficial effect.Preferred enzyme is that lytic enzyme is as proteolytic enzyme, amylase and lipase.What be highly preferred for that inventory dishwashing washs is amylase and/or proteolytic enzyme, comprises type and the modification type of current commercially available acquisition.Herein can comprise about 0.001 % by weight to about 10 % by weight containing enzyme composition, preferably about 0.005 % by weight to about 8 % by weight, the most preferably from about enzyme of 0.01 % by weight to about 6 % by weight.

Composition herein also optionally can comprise one or more transition-metalselective sequestrants, " sequestrant " or " chelating reagent ", such as iron and/or copper and/or manganese sequestrant.Be applicable to the group of the following composition of the optional freedom of sequestrant herein: the aromatic chelating agent of aminocarboxylate, phosphonate (especially amino phosphonates do), multifunctional replacement and their mixture.Can be used for business sequestrant herein comprise BEQUEST series and derive from Monsanto, DuPont and Nalco, the sequestrant of Inc.

Described detergent composition is preferably low whipability, be soluble in washing medium, and being of value to most the most effective under the pH value improving clean-up performance, such as, at about pH6.5 to about pH12.5, and in the optimum range of preferably about pH7.0 to about pH12.0, more preferably from about pH8.0 to about pH12.0.Be selected from sodium hydroxide or potassium hydroxide, sodium carbonate or salt of wormwood or concentrated crystal soda or sesquialter salt of wormwood, water glass or potassium silicate, boric acid, sodium bicarbonate or saleratus, Sodium Tetraborate or potassium borate and their mixture pH regulator components suitable.

One embodiment of the invention relate to gel detergent compositions, described composition comprises organic solvent, and described organic solvent is selected from by the following group formed: low molecular weight aliphatic or aromatic alcohol, lower molecular weight alkylene glycol, lower molecular weight alkylene glycol ether, low-molecular-weight ester, lower molecular weight alkylene amines, low molecular weight chain alkanolamine and their mixture.

Any ancillary component of any amount can be used in gel detergent compositions.Such as, the group of the following composition of the optional freedom of ancillary component: nano particle, Functionalized Surface Molecules, polymkeric substance, tensio-active agent, cosurfactant, metal ion, protein, dyestuff, acid, optical whitening agent, tinting material, filling salt, hydrotropic agent, sanitas, antioxidant, sterilant, mycocide, coloured patch, solubilizing agent, carrier and their mixture.

Very typically, herein cleaning compositions as laundry detergent, clothes washing agent addition agent, hard surface cleaners, synthesis with soap base washing soap slab, fabric softener and fabric treating liquid, fabric treating solid and various multiple treatment articles, some auxiliary agents will be needed, although some product simply prepared, may only needs as bleached additive, such as, oxygen bleaching agent and tensio-active agent as herein described.Suitable washing or the full list of clean auxiliary substance are found in WO99/05242.

Common cleaning additive comprises (not comprising any defined material above) such as washing assistant, enzyme, the polymkeric substance do not discussed above, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, catalytic species.Other cleaning additive can comprise short infusion herein, suds suppressor (defoamer) etc., except above-mentioned various activeconstituents except those or dedicated substances are as dispersed polymeres (such as deriving from BASFCorp. or Rohm & Haas), coloured patch, silverware nursing agent, antirust and/or inhibitor, dyestuff, filler, sterilant, alkalinity source, hydrotropic agent, antioxidant, enzyme stabilizers, front spices, spices, solubilizing agent, carrier, processing aid, pigment, and for liquid preparation, solvent can be comprised, sequestrant, dye transfer inhibitor, dispersion agent, whitening agent, suds suppressor, dyestuff, structure elasticizing agent, fabric softener, anti scuffing agent, hydrotropic agent, processing aid, and other fabric care agent, surface and skin-care agent.The embodiment that other cleaning additive above-mentioned is suitable and consumption are found in United States Patent (USP) 5,576,282,6,306,812B1 and 6,326,348B1 in.

Above-mentioned laundry detergent or cleaning compositions preferably comprise clean supplementary additive, and described additive is selected from by the following group formed: enzyme, alkali washing assistant, sequestrant builder materials, SYNTHETIC OPTICAL WHITNER, bleaching assistant, spices, defoamer, sterilant, corrosion inhibitor and their mixture.

using method

The present invention includes the method for clean target surface.As used herein, " target surface " can comprise such surface, such as fabric, dish, glasswork and other cooking surface, hard surface, hair or skin.As used herein, " hard surface " comprises the hard surface be present in typical household, such as hardwood, ceramic tile, pottery, plastics, leather, metal, glass.Aforesaid method comprises step: contacted with target surface at least partially by the composition (with pure substance form or be diluted in washing liq) comprising the polyol of modification, then optionally this target surface of rinsing.Preferably, described target surface is made to carry out washing step before above-mentioned optional rinse step.For the purposes of the present invention, washing includes but not limited to scouring, wiping and mechanical stirring.

As skilled in the art will recognize, cleaning compositions of the present invention is ideally suited in care and household (hard surface cleaning composition) and/or clothes washing application.

Select the pH of described composition solution, to be suitable for target surface to be cleaned to greatest extent, can cross over wide pH scope is about 5 to about 11.For personal care as skin and hair cleaning, the pH of this composition preferably has the pH of about 5 to about 8, and for clothes washing cleaning compositions, pH is about 8 to about 10.The strength of solution that described composition preferably uses is for about 200ppm is to about 10,000ppm.Water temperature range is preferably about 5 DEG C to about 100 DEG C.

For in clothes washing cleaning compositions, solution (or washing liq) concentration that described composition preferably uses is about 200ppm to about 10000ppm.Water temperature range is preferably about 5 DEG C to about 60 DEG C.The ratio of water and fabric is preferably about 1:1 to about 20:1.

Described method can comprise the step of the nonwoven substrate that contact is soaked into by present composition embodiment.As used herein, " nonwoven substrate " can comprise nonwoven sheet or the net material of any common style, and described sheet material or net material have suitable basic weight, thickness (thickness), absorptivity and strength characteristics.The embodiment of suitable commercially available matrix of nonwoven filament comprises DuPont with trade(brand)name with JamesRiverCorp. with trade(brand)name sell those.

As approved in those skilled in the art, detergent composition of the present invention is ideally suited in liquid dish cleaning compositions.Use the method for liquid dish composition of the present invention to comprise to make the step that soiled dishes contacts with the liquid dish cleaning compositions of the present invention of the usual about 0.5mL to about 20mL (often processing 25 dish) of the significant quantity be diluted in water.

Except of the present invention containing except sulfonate group multipolymer (or polymer composition), said detergent composition also can comprise other detergent builder.Other detergent builder have no particular limits.But such as alkaline auxiliary lotion can be enumerated as carbonate, supercarbonate and silicate, tri-polyphosphate, pyrophosphate salt, saltcake, nitrilotriacetic acid(NTA) salt, edetate, Citrate trianion, (methyl) acrylate copolymer salt, acid-co-maleic acid, fumarate, inner complex washing assistant is as zeolite, and the carboxy derivatives of polysaccharide is as carboxymethyl cellulose.With regard to regard to the counter ion in above-mentioned washing assistant, specifiable is basic metal as sodium or potassium and ammonium and amine.

With regard to the blending ratio of all above-mentioned additives and other detergent builder, relative to the detergent composition of 100 quality %, be generally suitably 0.1-50 quality %.More preferably 0.2-40 quality %.Even more preferably 0.3-35 quality %.Especially preferably 0.4-30 quality %, and most preferably 0.5 to 20 quality %.If additive/other detergent builder blending amount is less than 0.1 quality %, then there is the risk that cannot manifest the abundant effect of washing composition.If it is more than 50 quality %, then there is the risk that economy reduces.

Except synthesis type household detergent, for except the industrial detergent of yarn fabric industry etc. and hard surface cleaners, said detergent composition concept also comprise only for the washing composition of specific end use as bleach detergent, wherein effect of their a kind of components has been reinforced.

When said detergent composition is liquid detergent composition, kaolin turbidity is preferably 200mg/L or lower.More preferably 150mg/L or lower.Even more preferably 120mg/L or lower.Especially preferably 100mg/L or lower, and most preferably 50mg/L or lower.

kaolin turbidimetry method

The sample (liquid washing agent) of uniform stirring is positioned in 50 square millimeters of ponds of thick 10mm.After removal bubble, use the NDH2000 (name of product: turbidometer) manufactured by NipponDenshokuCo., Ltd, at 25 DEG C, measure turbidity (kaolin turbidity: mg/L).

Just can with regard to the enzyme blended with said detergent composition, desirably proteolytic enzyme, lipase and cellulase.Wherein, preferably there is in alkaline detergent solution highly active proteolytic enzyme, alkaline lipase and alkali cellulose enzyme.

Relative to the detergent composition of 100 quality %, the add-on of above-mentioned enzyme is suitably 5 quality % or lower.If it is more than 5 quality %, then no longer observe the improvement of washing composition effect, and there is the risk of economy reduction.

With regard to above-mentioned alkaline auxiliary lotion, desirably silicate, carbonate and vitriol.With regard to above-mentioned inner complex washing assistant, desirably diglycollic acid, hydroxycarboxylate (oxycarboxylatesalts), EDTA (edetate), DTPA (diethylentriamine pentacetate), STPP (tripoly phosphate sodium STPP) and citric acid.Except multipolymer of the present invention, also can use other water soluble polycarboxylic acid salt polymkeric substance.

Said detergent composition has excellent dispersiveness, has the reduction that extraordinary performance makes not easily to occur during standing storage performance, and not easily Impurity deposition occurs when storing at low temperatures, and can be used as the washing composition with excellent stability.

The present invention also comprises burnisher, and described burnisher comprises nonwoven substrate and above-mentioned laundry detergent or cleaning compositions.

Embodiment

By enumerating application embodiment, hereafter further illustrate the present invention.But the present invention is not limited only to these application embodiments.Except as otherwise noted, " number " refers to " mass parts ", and " % " refers to " quality % ".

The weight-average molecular weight, deposition rejection ability etc. of the present invention containing sulfonate group multipolymer is measured by following method.

weight-average molecular weight condition determination

Device: the L-7000 series manufactured by HitachiCo.

Detector: RI

Pillar: SHODEXAsahipakGF-310-HQ, GF-710-HQ, GF-IG7B of being manufactured by ShowaDenkoCo.

Column temperature: 40 DEG C

Flow: 0.5mL/min

Working curve: the polyacrylic acid standard substance prepared by SowaKagakuCo., Ltd.

Elute soln: 0.1N sodium acetate/acetonitrile=3/1 (weight ratio)

deposition rejection ability (LAS-Ca salt sedimentation rejection ability) measuring method

(1) pure water is joined in 9.3793g glycine, 9.6452g sodium-chlor and 5.1975g sodium hydroxide, and be supplemented to 1000.0g, and prepare glycine buffer.

(2) pure water is joined in glycine buffer obtained in 1.50g15% (w/w) Sodium dodecylbenzene sulfonate (LAS) aqueous solution, 0.80g sodium sulfate and 11.25g (1), and be supplemented to 500.0g.

(3) the sample polymer aqueous solution of obtained 0.1% (w/w).

(4) the CALCIUM CHLORIDE DIHYDRATE aqueous solution of obtained IM.

(5) in 100mL beaker, the 0.1% sample polymer aqueous solution, 8.20g pure water and 80.00g (2) obtained in 1.80g (3) is added, with obtained test soln.

(6) in described test soln, drip the 1M CALCIUM CHLORIDE DIHYDRATE aqueous solution obtained in (4) and stir, and measuring the change of turbidity.For measuring, use the autotitrator (major parts: COM-550, brightness measured parts: M-500) manufactured by HiranumaSangyo.Measure the turbidity change with transmission change under 650nm wavelength.

(7) transmission when being 0.270mL by the add-on of the IM CALCIUM CHLORIDE DIHYDRATE aqueous solution is called precipitation rejection ability.Be worth higher, precipitation rejection ability is better.

the measuring method of solid in polymer composition

Under nitrogen atmosphere, polymer composition (1.0g polymer composition+3.0g water) is placed in the baking oven being heated to 130 DEG C, and dry 1 hour.By the changes in weight difference of dry front and back, calculate solid (%) and volatile constituent (%).

ether-containing key monomer synthesize embodiment 1

To in the removable glass flask of 500mL volume being equipped with agitator (blade), add 81.2gNewcole2305 and (obtained by NipponNyukazaiCo., Ltd.; 5 moles of ethylene oxide adductss of C12-13 alcohol) and 16.8g potassium hydroxide (being hereafter also called " KOH ").Blast nitrogen, and temperature rises to 120 DEG C, stirs simultaneously.By this state is kept 1h, reaction system is dewatered.Then reflux exchanger is connected.Temperature is reduced to 60 DEG C.27.0g methallyl chloride (being hereafter also called MLC) is added, following reaction 5h in 30min.200.0g pure water is added in this, and after reaction 1h, with sulfuric acid neutralization [described mixture].After being cooled to room temperature, this aqueous solution is transferred in 500mL separating funnel, make it leave standstill until layering, and remove lower floor.Remaining upper strata is transferred in 300mL Florence flask, and removes solvent with rotatory evaporator.Removing by filtering the salt deposited, obtaining monomer 1.

application embodiment 1

To in the removable glass flask of 1000mL volume being equipped with reflux exchanger and agitator (blade), add 55.0g pure water and 0.0122g Mohr's salt, and temperature is risen to 90 DEG C, stir simultaneously, and by [this] as polymerization reaction system.Then, while stirring, to the polymerization reaction system remaining on 90 DEG C, the acrylic acid aqueous solution (being hereafter also called " 80%AA ") of 200.0g80% is dripped from different nozzles, the aqueous sodium hydroxide solution (being hereafter also called " 48%NaOH ") of 9.3g48%, 3-allyloxy-2-hydroxy-propanesulfonic acid sodium water solution (being hereafter also called " 40%HAPS ") of 75.0g40%, 10.0g monomer 1, the sodium persulfate aqueous solution (being hereafter also called " 15%NaPS ") of 47.6g15%, with the aqueous solution of sodium bisulfite (being hereafter also called " 35%SBS ") of 34.0g35%.The time for adding of corresponding solution is, 80%AA and 48%NaOH is 180min, 40%HAPS and monomer 1 be 120min, 15%NaPS is 190min, and 35%SBS is 175min.The drop rate of various solution is constant, and implements the dropping of various solution continuously.

Drip completely at 80%AA, above-mentioned reaction soln is kept 30 minutes (solidification) at 90 DEG C again, and terminates polyreaction.After completion of the polymerization reaction, stirring and make polymeric reaction solution cool while, slowly drip 148.1g48%NaOH, and in and polymeric reaction solution.

In this way, the aqueous solution (polymer composition 1) that the weight-average molecular weight with 44.9% solids concn is the polymkeric substance 1 (containing sulfonate group copolymer 1) of 12,000 is obtained.

application embodiment 2

To in the removable glass flask of 1000mL volume being equipped with reflux exchanger and agitator (blade), add 69.0g pure water, 30.0g monomer 1 and 0.0121g Mohr's salt, and temperature is risen to 90 DEG C, stir, and by [this] as polymerization reaction system simultaneously.Then, while stirring, to the polymerization reaction system remaining on 90 DEG C, 175.0g80%AA, 8.1g48%NaOH, 75.0g40%HAPS, 42.9g15%NaPS and 42.9g35%SBS is dripped from different nozzles.The time for adding of corresponding solution is, 80%AA and 48%NaOH is 180min, 40%HAPS be 120min, 15%NaPS is 190min, and 35%SBS is 175min.The drop rate of various solution is constant, and implements the dropping of various solution continuously.

Drip completely at 80%AA, above-mentioned reaction soln is kept 30 minutes (solidification) at 90 DEG C again, and terminates polyreaction.After completion of the polymerization reaction, stirring and make polymeric reaction solution cool while, slowly drip 129.6g48%NaOH, and in and polymeric reaction solution.

In this way, the aqueous solution (polymer composition 2) that the weight-average molecular weight with 45.0% solids concn is the polymkeric substance 2 (containing sulfonate group multipolymer 2) of 19,000 is obtained.

ether-containing key monomer synthesize embodiment 2

To in the removable glass flask of 500mL volume being equipped with reflux exchanger and agitator (blade), add 370.0g propyl carbinol and 4.27gKOH.While stirring, temperature is risen to 90 DEG C.Then, in 30 minutes, add 57.0g glycidyl allyl ether (being hereafter also called " AGE "), then react 5h.Be cooled to room temperature and with in sulfuric acid and after, this aqueous solution is transferred in 1000mL Florence flask, and removes solvent with rotatory evaporator.In this, add 200.0g pure water, and this aqueous solution is transferred in 500mL separating funnel, make it leave standstill until layering, and remove lower floor.Remaining upper strata is transferred in 300mL Florence flask, and removes solvent with rotatory evaporator.Removing by filtering the salt deposited, obtaining monomer 2.

application embodiment 3

To in the removable glass flask of 1000mL volume being equipped with reflux exchanger and agitator (blade), add 57.0g pure water and 0.0178g Mohr's salt, and temperature is risen to 90 DEG C, stir simultaneously, and by [this] as polymerization reaction system.Then, while stirring, to the polymerization reaction system remaining on 90 DEG C, 225.0g80%AA, 10.4g48%NaOH, 225.0g40%HAPS, 30.0g monomer 2,61.4g15%NaPS and 70.2g35%SBS is dripped from different nozzles.The time for adding of corresponding solution is, 80%AA and 48%NaOH is 180min, 40%HAPS and monomer 2 be 120min, 15%NaPS is 190min, and 35%SBS is 175min.The drop rate of various solution is constant, and implements the dropping of various solution continuously.

Drip completely at 80%AA, above-mentioned reaction soln is kept 30 minutes (solidification) at 90 DEG C again, and terminates polyreaction.After completion of the polymerization reaction, stirring and make polymeric reaction solution cool while, slowly drip 166.7g48%NaOH, and in and polymeric reaction solution.

In this way, the aqueous solution (polymer composition 3) that the weight-average molecular weight with 44.8% solids concn is the polymkeric substance 3 (containing sulfonate group multipolymer 3) of 15,000 is obtained.

ether-containing key monomer synthesize embodiment 3

To in the removable glass flask of 500mL volume being equipped with reflux exchanger and agitator (blade), add 1 moles of ethylene oxide adducts (being hereafter also called " MLAl ") and the 1.8gKOH of 34.8g methallyl alcohol.While stirring, temperature is risen to 90 DEG C.Then, in 30min, add 55.8g2-ethylhexyl glycidyl ether (being hereafter also called " EHGE "), then react 5h.200.0g pure water is added in this, and after reaction 1h, with sulfuric acid neutralization [described mixture].After being cooled to room temperature, this aqueous solution is transferred in 500mL separating funnel, make it leave standstill until layering, and remove lower floor.Remaining upper strata is transferred in 300mL Florence flask, and removes solvent with rotatory evaporator.Removing by filtering the salt deposited, obtaining monomer 3.

application embodiment 4

To in the removable glass flask of 1000mL volume being equipped with reflux exchanger and agitator (blade), add 39.0g pure water and 0.0119g Mohr's salt, and temperature is risen to 90 DEG C, stir simultaneously, and by [this] as polymerization reaction system.Then, while stirring, to the polymerization reaction system remaining on 90 DEG C, 150.0g80%AA, 6.9g48%NaOH, 150.0g40%HAPS, 20.0g monomer 3,40.2g15%NaPS and 45.9g35%SBS is dripped from different nozzles.The time for adding of corresponding solution is, 80%AA and 48%NaOH is 180min, 40%HAPS and monomer 3 be 120min, 15%NaPS is 190min, and 35%SBS is 175min.The drop rate of various solution is constant, and implements the dropping of various solution continuously.

Drip completely at 80%AA, above-mentioned reaction soln is kept 30 minutes (solidification) at 90 DEG C again, and terminates polyreaction.After completion of the polymerization reaction, stirring and make polymeric reaction solution cool while, slowly drip 111.1g48%NaOH, and in and polymeric reaction solution.

In this way, the aqueous solution (polymer composition 4) that the weight-average molecular weight with 44.7% solids concn is the polymkeric substance 4 (containing sulfonate group multipolymer 4) of 16,000 is obtained.

ether-containing key monomer synthesize embodiment 4

To in the removable glass flask of 500mL volume being equipped with reflux exchanger and agitator (blade), add 46.4gMLAl and 2.0gKOH.While stirring, temperature is risen to 90 DEG C.Then, in 30min, add 52.0g n-butyl glycidyl ether (being hereafter also called " BGE "), then react 5h.200.0g pure water is added in this, and after reaction 1h, with sulfuric acid neutralization [described mixture].After being cooled to room temperature, this aqueous solution is transferred in 500mL separating funnel, make it leave standstill until layering, and remove lower floor.Remaining upper strata is transferred in 300mL Florence flask, and removes solvent with rotatory evaporator.Removing by filtering the salt deposited, obtaining monomer 4.

application embodiment 5

To in the removable glass flask of 1000mL volume being equipped with reflux exchanger and agitator (blade), add 84.0g pure water, 40.0g monomer 4 and 0.0121g Mohr's salt, and temperature is risen to 90 DEG C, stir, and by [this] as polymerization reaction system simultaneously.Then, while stirring, to the polymerization reaction system remaining on 90 DEG C, 175.0g80%AA, 8.1g48%NaOH, 50.0g40%HAPS, 44.0g15%NaPS and 44.0g35%SBS is dripped from different nozzles.The time for adding of corresponding solution is, 80%AA and 48%NaOH is 180min, 40%HAPS be 120min, 15%NaPS is 185min, and 35%SBS is 175min.The drop rate of various solution is constant, and implements the dropping of various solution continuously.

Drip completely at 80%AA, above-mentioned reaction soln is kept 30 minutes (solidification) at 90 DEG C again, and terminates polyreaction.After completion of the polymerization reaction, stirring and make polymeric reaction solution cool while, slowly drip 129.6g48%NaOH, and in and polymeric reaction solution.

In this way, the aqueous solution (polymer composition 5) that the weight-average molecular weight with 44.8% solids concn is the polymkeric substance 5 (containing sulfonate group multipolymer 5) of 16,000 is obtained.

ether-containing key monomer synthesize embodiment 5

To in the removable glass flask of 500mL volume being equipped with agitator (blade), add 63.6gNewcole2303 and (obtained by NipponNyukazaiCo., Ltd.; 3 moles of ethylene oxide adductss of C12-13 alcohol) and 16.8gKOH.Blast nitrogen, and temperature rises to 120 DEG C, stirs simultaneously.By this state is kept 1h, reaction system is dewatered.Then reflux exchanger is connected.Temperature is reduced to 60 DEG C.In 30min, add 27.0gMLC, then react 5h.200.0g pure water is added in this, and after reaction 1h, with sulfuric acid neutralization [described mixture].After being cooled to room temperature, this aqueous solution is transferred in 500mL separating funnel, make it leave standstill until layering, and remove lower floor.Remaining upper strata is transferred in 300mL Florence flask, and removes solvent with rotatory evaporator.Removing by filtering the salt deposited, obtaining monomer 5.

application embodiment 6

To in the removable glass flask of 1000mL volume being equipped with reflux exchanger and agitator (blade), add 30.0g pure water and 0.0120g Mohr's salt, and temperature is risen to 90 DEG C, stir simultaneously, and by [this] as polymerization reaction system.Then, while stirring, to the polymerization reaction system remaining on 90 DEG C, 162.5g80%AA, 7.5g48%NaOH, 150.0g40%HAPS, 10.0g monomer 5,42.1g15%NaPS and 48.1g35%SBS is dripped from different nozzles.The time for adding of corresponding solution is, 80%AA and 48%NaOH is 180min, 40%HAPS and monomer 5 be 120min, 15%NaPS is 185min, and 35%SBS is 175min.The drop rate of various solution is constant, and implements the dropping of various solution continuously.

Drip completely at 80%AA, above-mentioned reaction soln is kept 30 minutes (solidification) at 90 DEG C again, and terminates polyreaction.After completion of the polymerization reaction, stirring and make polymeric reaction solution cool while, slowly drip 120.4g48%NaOH, and in and polymeric reaction solution.

In this way, the aqueous solution (polymer composition 6) that the weight-average molecular weight with 44.8% solids concn is the polymkeric substance 6 (containing sulfonate group multipolymer 6) of 14,000 is obtained.

ether-containing key monomer synthesize embodiment 6

To in the removable glass flask of 500mL volume being equipped with agitator (blade), add 61.2gNewcole1004 and (obtained by NipponNyukazaiCo., Ltd.; 4 moles of ethylene oxide adductss of 2-Ethylhexyl Alcohol) and 16.8gKOH.Blast nitrogen, and temperature rises to 120 DEG C, stirs simultaneously.By this state is kept 1h, reaction system is dewatered.Then reflux exchanger is connected.Temperature is reduced to 60 DEG C.In 30min, add 27.0gMLC, then react 5h.200.0g pure water is added in this, and after reaction 1h, with sulfuric acid neutralization [described mixture].After being cooled to room temperature, this aqueous solution is transferred in 500mL separating funnel, make it leave standstill until layering, and remove lower floor.Remaining upper strata is transferred in 300mL Florence flask, and removes solvent with rotatory evaporator.Removing by filtering the salt deposited, obtaining monomer 6.

application embodiment 7

To in the removable glass flask of 1000mL volume being equipped with reflux exchanger and agitator (blade), add 54.0g pure water and 0.0121g Mohr's salt, and temperature is risen to 90 DEG C, stir simultaneously, and by [this] as polymerization reaction system.Then, while stirring, to the polymerization reaction system remaining on 90 DEG C, 175.0g80%AA, 8.1g48%NaOH, 100.0g40%HAPS, 20.0g monomer 6,43.6g15%NaPS and 43.6g35%SBS is dripped from different nozzles.The time for adding of corresponding solution is, 80%AA and 48%NaOH is 180min, 40%HAPS and monomer 6 be 120min, 15%NaPS is 185min, and 35%SBS is 175min.The drop rate of various solution is constant, and implements the dropping of various solution continuously.

Drip completely at 80%AA, above-mentioned reaction soln is kept 30 minutes (solidification) at 90 DEG C again, and terminates polyreaction.After completion of the polymerization reaction, stirring and make polymeric reaction solution cool while, slowly drip 129.6g48%NaOH, and in and polymeric reaction solution.

In this way, the aqueous solution (polymer composition 7) that the weight-average molecular weight with 45.0% solids concn is the polymkeric substance 7 (containing sulfonate group multipolymer 7) of 18,000 is obtained.

application embodiment 8

To in the removable glass flask of 1000mL volume being equipped with reflux exchanger and agitator (blade), add 100.1g pure water and 12.0g monomer 1, and temperature is risen to 90 DEG C, stir simultaneously, and by [this] as polymerization reaction system.Then, while stirring, to the polymerization reaction system remaining on 90 DEG C, 90.0g80%AA, 90.0g40%HAPS and 31.7g15%NaPS is dripped from different nozzles.The time for adding of corresponding solution is, 80%AA is 90min, 40%HAPS is 60min, and 15%NaPS is 110min.The drop rate of various solution is constant, and implements the dropping of various solution continuously.

Drip completely at 80%AA, above-mentioned reaction soln is kept 60 minutes (solidification) at 90 DEG C again, and terminates polyreaction.After completion of the polymerization reaction, while polymeric reaction solution is cooled, slowly drip 70.8g48%NaOH and 30.0g pure water in stirring, and neutralization and dilution polymeric reaction solution.

In this way, the aqueous solution (polymer composition 8) that the weight-average molecular weight with 36.2% solids concn is the polymkeric substance 8 (containing sulfonate group multipolymer 8) of 95,000 is obtained.

comparing embodiment 1

To in the removable SUS flask of 2500mL volume being equipped with reflux exchanger and agitator (blade), add 125.0g pure water and 0.0220g Mohr's salt, and temperature is risen to 90 DEG C, stir simultaneously, and by [this] as polymerization reaction system.Then, while stirring, to the polymerization reaction system remaining on 90 DEG C, drip 315.0g80%AA, 180.0g40%HAPS, 36.0g vinylbenzene (being hereafter also called " St "), 83.6g15%NaPS and 71.6g35%SBS from different nozzles.The time for adding of corresponding solution is, 80%AA is 180min, 40%HAPS and St be 150min, 15%NaPS is 190min, and 35%SBS is 175min.The drop rate of various solution is constant, and implements the dropping of various solution continuously.

Drip completely at 80%AA, above-mentioned reaction soln is kept 30 minutes (solidification) at 90 DEG C again, and terminates polyreaction.After completion of the polymerization reaction, stirring and make polymeric reaction solution cool while, slowly drip 247.9g48%NaOH, and in and polymeric reaction solution.In this way, the aqueous solution (comparative polymers composition 1) that the weight-average molecular weight with 44.8% solids concn is the polymkeric substance (comparative polymers 1) of 14,000 is obtained.

comparing embodiment 2

To in the removable SUS flask of 2500mL volume being equipped with reflux exchanger and agitator (blade), add 84.0g pure water and 0.0219g Mohr's salt, and temperature is risen to 90 DEG C, stir simultaneously, and by [this] as polymerization reaction system.Then, while stirring, to the polymerization reaction system remaining on 90 DEG C, drip 315.0g80%AA, 14.5g48%NaOH, 225.0g40%HAPS, 18.0g butyl acrylate (being hereafter also called " BA "), 81.1g15%NaPS and 69.5g35%SBS from different nozzles.The time for adding of corresponding solution is, 80%AA and 48%NaOH is 180min, 40%HAPS and BA be 150min, 15%NaPS is 190min, and 35%SBS is 175min.The drop rate of various solution is constant, and implements the dropping of various solution continuously.

Drip completely at 80%AA, above-mentioned reaction soln is kept 30 minutes (solidification) at 90 DEG C again, and terminates polyreaction.After completion of the polymerization reaction, stirring and make polymeric reaction solution cool while, slowly drip 233.3g48%NaOH, and in and polymeric reaction solution.

In this way, the aqueous solution (comparative polymers composition 2) that the weight-average molecular weight with 44.5% solids concn is the polymkeric substance (comparative polymers 2) of 7500 is obtained.

application embodiment 9

In application embodiment 9, adopt aforesaid method, the deposition rejection ability of the polymkeric substance obtained in embodiment 1-7 and comparing embodiment 1 and 2 is applied in evaluation.The results are summarized in table 1.

table 1

Clearly visible from table 1, compared with the comparative polymers composition comprising comparative polymers, polymer composition of the present invention has significantly excellent deposition rejection ability, and described comparative polymers does not comprise ehter bond monomer as hydrophobic monomer.

composite preparation

granular laundry detergent embodiment 10

¹as applied for the multipolymer according to any one of embodiment 1,2,3,4,5,6,7 or 8

granular laundry detergent embodiment 11

aqueous slurry composition

¹as applied for any mixture of multipolymer according to any one of embodiment 1,2,3,4,5,6,7 or 8 or multipolymer.

the preparation of spray-dired powder

The aqueous slurry of preparation containing above-mentioned composition, its water content is 25.89%.Described aqueous slurry is heated to 72 DEG C, then at high pressure (from 5.5 × 10 ⁶nm ^-2to 6.0 × 10 ⁶nm ^-2) under pump to be drawn to temperature of inlet air be in the Countercurrent Spray Dryer of 270 DEG C to 300 DEG C.Described aqueous slurry is atomized, then makes the slurry dried after atomization with obtained solid mixture, then cooled and sieve to remove especially big material (>1.8mm), thus forming free-pouring spray-dired powder.The waste gas of tiny material (<0.15mm) in spray-drying tower is eluriated, and is then collected in the containment system after tower.The water content of described spray-dried powders is 1.0% weight, and bulk density is 427g/l, and size distribution makes the particle diameter of the spray-dried powders of 95.2% weight be 150 to 710 microns.Provide the composition of this spray-dired powder below.

Spray-dired powder composition.

¹as applied for any mixture of multipolymer according to any one of embodiment 1,2,3,4,5,6,7 or 8 or multipolymer.

the preparation of anionic surfactant granules 1

Use Tilt-A-Pin, then use Tilt-A-Plow agitator (manufacturing by Processall), with 520g batch reference system for anionic detersive surfactant particle 1.The 108g sodium sulfate provided is joined in Tilt-A-Pin agitator together with 244g sodium carbonate.By the C of 168g70% activity ₂₅e ₃s paste is (based on C _12/15the ethoxylated sulfate of alcohol and oxyethane) join in Tilt-A-Pin agitator.Then, under 1200rpm, described component is stirred 10 seconds.Then, by gained powder transfer in Tilt-A-Plow agitator, and stir 2 minutes at 200 rpm, to form particle.Then make described particle dry in the fluid bed dryer of 120 DEG C with the speed of 2500 liters/min, until the equilibrium relative humidity of described particle is less than 15%.Then dry granules is sieved, and by by 1180 μm and the part staying 250 μm remain.Anionic detersive surfactant particle 1 composed as follows shown in:

The C of 25.0% w/w ₂₅e ₃s ethoxylated sulfate

The sodium sulfate of 18.0% w/w

The sodium carbonate of 57.0% w/w

the preparation of cationic detersive surfactant particle 1

On MortonFM-50Loedige agitator, with 14.6kg batch for benchmark, preparation cationic surfactant granules 1.4.5kg micronised sodium sulphate and 4.5kg micronization sodium carbonate are mixed in MortonFM-50Loedige agitator in advance.By the activity one-C of 4.6kg40% _12-14alkyl one-hydroxyethyl dimethyl quaternary ammonium muriate (cats product) aqueous solution joins in MortonFM-50Loedige agitator, makes main drive simultaneously and cut to mix device running.After approximately two minutes of mixing, the mixture being 1:1 by 1.0kg micronised sodium sulphate and micronization sodium carbonate weight ratio joins in agitator.Collect the agglomerate of gained, and use fluid bed dryer with 2500 liters/min of air for benchmark, drying 30 minutes at 100 DEG C to 140 DEG C.By gained powder sieving, and collect by the part of 1400 μm as cationic surfactant granules 1.Cationic surfactant granules 1 composed as follows shown in:

One C of 15% w/w _12-14alkyl one hydroxyethyl dimethyl aliquat

The sodium carbonate of 40.76% w/w

The sodium sulfate of 40.76% w/w

The moisture of 3.48% w/w and other composition

the preparation of granular laundry detergent composition

Spray-dried powders in 10.84kg embodiment 6,4.76kg anionic detersive surfactant particle 1,1.57kg cationic detersive surfactant particle 1 and 7.83kg (total amount) other independent feed dry is added material join a diameter 1m with in the concrete batch agitator of 24rpm operate.When all substances are all added into after in agitator, described mixture is stirred 5 minutes, to form granular laundry detergent composition.The formula of granular laundry detergent composition is as described below:

granular laundry detergent composition

liquid laundry detergent embodiment 12

Composition	A	B	C	D	E
							wt％	wt％	wt％	wt％	wt％
Sodium alkylether sulphate	14.4％		9.2％	5.4％
						Linear alkyl benzene sulphonic acid	4.4％	12.2％	5.7％	1.3％
Alkylethoxylate	2.2％	8.8％	8.1％	3.4％
						Amine oxide	0.7％	1.5％
Citric acid	2.0％	3.4％	1.9％	1.0％	1.6％
						Lipid acid	3.0％	8.3％			16.0％
Proteolytic enzyme	1.0％	0.7％	1.0％		2.5％
						Amylase	0.2％	0.2％			0.3.％
Borax	1.5％	2.4％	2.9％		29 -->
						Calcium formiate and sodium formiate	0.2％
Formic acid					1.1％
						Multipolymer 1	1.8％	2.1％			3.2％
Sodium polyacrylate				0.2％
						Sodium polyacrylate multipolymer			0.6％
White dyes	0.15％	0.2％	0.12％	0.12％	0.2％
						Ethanol	2.5％	1.4％	1.5％
Propylene glycol	6.6％	4.9％	4.0％		15.7％
						Sorbyl alcohol			4.0％
Thanomin	1.5％	0.8％	0.1％		11.0％
						Sodium hydroxide	3.0％	4.9％	1.9％	1.0％
Sodium cumene sulfonate		2.0％
						Silicone suds suppressor		0.01％
Spices	0.3％	0.7％	0.3％	0.4％	0.6％
						Opalizer 5		0.30％	0.20％		0.50％
Water	Surplus	Surplus	Surplus	Surplus	Surplus
							100.0％	100.0％	100.0％	100.0％	100.0％

¹as applied for any mixture of multipolymer according to any one of embodiment 1,2,3,4,5,6,7 or 8 or multipolymer.

²diethylene triaminepentaacetic acid(DTPA), sodium salt

³diethylenetriamine five methylenephosphonic acid, sodium salt

⁴ethylenediamine tetraacetic acid (EDTA), sodium salt;

⁵AcusolOP301

¹as applied for any mixture of multipolymer according to any one of embodiment 1,2,3,4,5,6,7 or 8 or multipolymer.

¹as applied for any mixture of multipolymer according to any one of embodiment 1,2,3,4,5,6,7 or 8 or multipolymer.

²pEG-PVA graft copolymer is the polyethylene oxide copolymer of polyvinyl acetate grafting, and it has polyethylene oxide main chain and multiple polyvinyl acetate ester side chain.The molecular weight of described polyethylene oxide main chain is about 6000, and the weight ratio of polyethylene oxide and polyvinyl acetate is about 40 to 60, and every 50 ethylene oxide units have and are no more than 1 grafting site.

³alco725 (phenylethylene ethylene/propenoic acid ester)

liquid hand dishwashing detergent embodiment 13

¹as applied for any mixture of multipolymer according to any one of embodiment 1,2,3,4,5,6,7 or 8 or polymkeric substance.

²non-ionic can be that any one comprises the C of 9 oxyethyl groups ₁₁the tensio-active agent of alkyl ethoxylated.

³1,3BAC is 1,3-bis-(methylamine)-hexanaphthene.

⁴methacrylic acid (N, N-dimethylamino) ethyl ester homopolymer

automatic dishwashing detergent embodiment 14

¹as derived from the SLF-18POLYTERGENT of BASFCorporation.

²multipolymer, as derived from Rohm & Haas 445N, or derive from iAlco's 725.

³ethoxylated cationic diamines, disclosed in U.S. Patent No. 4659802 those.

⁴as applied for any mixture of multipolymer according to any one of embodiment 1,2,3,4,5,6,7 or 8 or multipolymer.

inventory dishwashing washs unit dose products embodiment 15

Embodiment	A
		Granular composition
STPP	0
		Silicate	2-8
Carbonate	25-50
		Multipolymer 1	5-10
Polymeric dispersant 2	1-5
		Nonionogenic tenside 3	1-5
Enzyme	1-6
		SYNTHETIC OPTICAL WHITNER and bleach-activating agent	2.5-10
Spices	0.05-1
		Sodium sulfate	0-10
		Liquid composition
DPG	40-50

Nonionogenic tenside 3	40-50
		Neodol CllE9	0-5.0
Glycerine	0-5.0
		Dyestuff	0.1-1.0

¹as applied for any mixture of multipolymer according to any one of embodiment 1,2,3,4,5,6,7 or 8 or multipolymer.

²multipolymer is as derived from Rohm & Haas 445N, or derive from Alco's 725.

³as derived from the SLF-18POLYTERGENT of BASFCorporation.

Claims (2)

1. a laundry detergent or cleaning compositions, described laundry detergent or cleaning compositions comprise the multipolymer containing sulfonate group, described multipolymer is by the structural unit (a) derived from one or more monomers (A) of 1 to 49 quality %, but 50 quality % or more are still less than the structural unit (b) derived from carboxyl group-containing monomer (B) and 1 quality % or more of 98 quality % are less than forming as necessary component units derived from containing sulfonate group monomer (C) structural unit (c) of 49 quality %, described monomer (B) is selected from vinylformic acid and acrylate, the ether-containing key monomer that described monomer (A) selects free style (2) to represent,

In formula (2), R ₀represent hydrogen atom or CH ₃group, R represents CH ₂group, CH ₂cH ₂group or singly-bound, X represents the number of 0-5, and R ₁for hydrogen atom or C1 to the C20 organic group being selected from alkyl;

Wherein said laundry detergent or cleaning compositions are selected from by the following group formed: the automatic platter washing composition of liquid laundry detergent composition, solid laundry detergent composition, hard surface cleaning composition, liquid hand platter washing composition, the automatic platter washing composition of solid, the automatic platter washing composition of liquid and tablet/unit dosage;

Described washing composition or cleaning compositions comprise the copolymer compositions containing hydrophobic group of 1 % by weight to 20 % by weight;

Described washing composition or composition also comprises surfactant system, described surfactant system comprises C ₁₀-C ₁₅alkylbenzene sulfonate or C ₈-C ₁₈linear alkyl benzene sulphonic acid tensio-active agent; Described surfactant system also comprises one or more cosurfactants, and described cosurfactant is selected from by the following group formed: nonionogenic tenside, cats product, anion surfactant and their mixture; And

Described washing composition or composition also comprise clean supplementary additive, and described additive is selected from by the following group formed: enzyme, alkali washing assistant, sequestrant builder materials, SYNTHETIC OPTICAL WHITNER, bleaching assistant, spices, defoamer, sterilant, corrosion inhibitor and their mixture.

2. a burnisher, described burnisher comprises nonwoven substrate and laundry detergent as claimed in claim 1 or cleaning compositions.